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Determining the Liquid Light Scattering Cross Section and Depolarization Spectra Using Polarized Resonance Synchronous Spectroscopy

Athukorale, Sumudu A., Zhou, Yadong, Zou, Shengli, Zhang, Dongmao
Analytical chemistry 2017 v.89 no.23 pp. 12705-12712
1-propanol, acetone, acetonitrile, benzene, carbon disulfide, carbon tetrachloride, constitutional isomerization, cyclohexanes, dimethyl sulfoxide, dimethylformamide, ethanol, hexane, isomers, light scattering, liquids, methanol, pyridines, researchers, solvents, spectroscopy, tetrahydrofuran, toluene
Rayleigh scattering is a universal material property because all materials have nonzero polarizability. Reliable quantification of the material light scattering cross section in the liquid phase and its depolarization spectra is, however, challenging due to a host of sample and instrument issues. Using the recently developed polarized resonance synchronous spectroscopic method, we reported the light scattering cross section and depolarization spectra measured for a total of 29 liquids including water, methanol, ethanol, 1-propanol, 1-butanol, dimethylformamide, carbon disulfide, dimethyl sulfoxide, hexane and two hexane isomers (3-methylpentane and 2,3-dimethylbutane), tetrahydrofuran, cyclohexane, acetonitrile, pyridine, chloromethanes including di-, tri, tetrachloromethane, acetone, benzene and eight benzene derivatives (toluene, fluorobenzene, 1,2-, 1,3-, and 1,4-difluorobenzene, chlorobenzene, 1,2- and 1,3-dichlorobenzene, and nitrobenzene). The solvent light scattering depolarization is wavelength-independent for the model solvents, and it varies from 0.023 ± 0.011 for CCl₄ to 0.619 ± 0.022 for nitrobenzene. The light scattering cross-section spectra can be approximated with the function of σ(λ) = αλ–⁴ with the α value varying from 7.2 ± 0.2 × 10–⁴⁵ cm⁶ for water to a maximum of 8.5 ± 0.6 × 10–⁴³ cm⁶ for nitrobenzene. Structural isomerization has no significant effect on either the depolarization or the scattering cross sections for both hexanes and difluorobenzene isomers. This work represents the most comprehensive experimental study on liquid light scattering features. The insight from this work should be important for understanding the correlation between the material structure and optical properties. The described method can be readily implemented by researchers with access to conventional spectrofluorometers equipped with excitation and detection polarizers.